Methylamine → HCID 118098712, compound

HRID 708837Notes

Reaction equation

HRID 708837 reaction equation
[CH:1]1([S:4][C:5]2[C:12]([F:13])=[CH:11][C:10]([N+:14]([O-:16])=[O:15])=[CH:9][C:6]=2[CH:7]=O)[CH2:3][CH2:2]1.[CH3:17][NH2:18].[BH4-].[Na+].[CH3:21][C:22]([O:25][C:26]([O:28]C(OC(C)(C)C)=O)=O)([CH3:24])[CH3:23]>CO>[CH:1]1([S:4][C:5]2[C:12]([F:13])=[CH:11][C:10]([N+:14]([O-:16])=[O:15])=[CH:9][C:6]=2[CH2:7][N:18]([CH3:17])[C:26](=[O:28])[O:25][C:22]([CH3:24])([CH3:23])[CH3:21])[CH2:3][CH2:2]1

Participants

6

Reactant 4

HCID 6329MethylamineHCID 90495Di-tert-butyl dicarbonateHCID 4311764Sodium borohydrideHCID 118098711HCID 118098711, compound

Product 1

HCID 118098712HCID 118098712, compoundYield 73.8%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 11B (0.965 g, 4.00 mmol) in MeOH (20 mL) was added methylamine (33% in EtOH) (0.598 mL, 4.80 mmol). The mixture was stirred at rt for 1.5 h, then was cooled to 0° C. sodium borohydride (0.182 g, 4.80 mmol) was added, then the mixture was stirred at rt for 1 h, then was concentrated. The resultant residue was taken up in THF (20 mL) and was treated with sat. NaHCO3 (10 mL). The mixture was stirred at rt for 10 min, then was treated with Boc2O (1.048 g, 4.80 mmol). The mixture was stirred at rt for 2 h. The THF was removed in vacuo, then the aqueous phase was extracted with EtOAc. The organic phase was washed with H2O and brine, dried (Na2SO4) and concentrated. The crude product was purified by flash chromatography (loaded in chloroform onto a 80 g column and eluted with a gradient from 0 to 50% ethyl acetate/hexanes) to give 11C (1.05 g, 2.95 mmol, 73.6% yield) as an yellow oil. MS (ESI) m/z: 379.1 [M+Na]+; 1H NMR (400 MHz, chloroform-d) δ ppm 7.78-7.94 (2H, m), 4.57 (2H, br. s.), 2.90 (3H, s), 2.49 (1H, qd, J=7.2, 4.3 Hz), 1.38-1.53 (9H, m), 0.92-0.98 (2H, m), 0.62-0.68 (2H, m).

Workup

  1. additionwas added
  2. stirringthe mixture was stirred at rt for 1 h
  3. concentrationwas concentrated
  4. additionwas treated with sat. NaHCO3 (10 mL)
  5. stirringThe mixture was stirred at rt for 10 min
  6. stirringThe mixture was stirred at rt for 2 h
  7. customThe THF was removed in vacuo
  8. extractionthe aqueous phase was extracted with EtOAc
  9. washThe organic phase was washed with H2O and brine
  10. dry with materialdried (Na2SO4)
  11. concentrationconcentrated
  12. customThe crude product was purified by flash chromatography (
  13. washeluted with a gradient from 0 to 50% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-6a986c7e4edb4b2d995563c4ea76de05
Source dataset
uspto-grants-2015_11
Patent number
US09174974B2

Reaction notes

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